ES3009572T3 - Processes for producing fluorided solid oxides and uses thereof in metallocene-based catalyst systems - Google Patents

Abstract

Described herein are methods for preparing fluorinated solid oxides by contacting a fluorine-containing acidic compound with an inorganic base to form an aqueous mixture having a pH of at least about 4, followed by contacting a solid oxide with the aqueous mixture to produce the fluorinated solid oxide. Also described are methods for preparing fluorinated solid oxides by contacting a fluorine-containing acidic compound with a solid oxide to produce a mixture, followed by contacting the mixture with an inorganic base to produce the fluorinated solid oxide at a pH of at least about 4. The fluorinated solid oxide can be used as an activator component in a catalyst system for olefin polymerization. (Automatic translation with Google Translate, no legal value)

Description

DESCRIPTION

Processes for producing fluorinated solid oxides and their uses in metallocene-based catalyst systems

Reference to related request

This application claims the benefit of U.S. Provisional Patent Application No. 62/737,157 filed on September 27, 2018.

Background of the invention

The present invention relates generally to the field of olefin polymerization catalysis, supported catalyst compositions, and methods for the polymerization of olefins and polyolefins. More specifically, this invention relates to fluorinated solid oxides, methods for manufacturing fluorinated solid oxides, and catalyst compositions and polymerization processes employing these fluorinated solid oxides.

Fluorine compounds, such as hydrogen fluoride and hydrofluoric acid, are highly corrosive and can release harmful gases during processing. Therefore, it would be beneficial to use fluorine compounds to produce solid fluorinated oxides in a safer manner and with few or no emissions. Accordingly, it is to these ends that the present invention is generally directed.

Summary of the invention

This summary is provided to introduce, in a simplified form, a selection of concepts that are further described below in the detailed description. This summary is not intended to identify the required or essential characteristics of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the claimed subject matter.

Described and disclosed herein are processes for producing fluorinated solid oxides. A first process for producing a fluorinated solid oxide may comprise (a) contacting a fluorine-containing acidic compound and an inorganic base to produce an aqueous mixture having a pH of at least about 4, and (b) contacting a solid oxide with the aqueous mixture to produce the fluorinated solid oxide. A second process for producing a fluorinated solid oxide may comprise (A) contacting a fluorine-containing acidic compound with a solid oxide to produce a mixture; and (B) contacting the mixture with an inorganic base to produce the fluorinated solid oxide at a pH of at least about 4. In non-limiting aspects of this invention, the fluorine-containing acid compound may comprise tetrafluoroboric acid (HBF4) and/or hexafluorosilicic acid (H2SiF6), the inorganic base may comprise a zinc-containing base, such as ZnO, and the solid oxide may comprise silica-alumina and/or silica-coated alumina.

Catalyst compositions containing these fluorinated solid oxides are also provided. One such catalyst composition may comprise a metallocene compound, a fluorinated solid oxide, and an optional cocatalyst. The catalyst compositions can be used to polymerize olefins to form homopolymers, copolymers, terpolymers, and the like. A process for polymerizing olefins in the presence of a catalyst composition of the present invention may comprise contacting the catalyst composition with an olefin monomer and optionally an olefin comonomer in a polymerization reactor system, under polymerization conditions, to produce the olefin polymer.

Polymers produced from the polymerization of olefins, resulting in ethylene-based or propylene-based copolymers or homopolymers, for example, can be used to produce various manufactured goods.

Both the preceding summary and the following detailed description provide examples and are merely explanatory. Accordingly, the preceding summary and the following detailed description should not be considered restrictive. In addition, additional features or variations beyond those set forth herein may be provided. For example, certain aspects may relate to various combinations and subcombinations of features described in the detailed description.

Brief description of the figures

FIG. 1 presents a graph of the particle size distribution of the fluorinated solid oxide of Example 15.

FIG. 2 presents a scanning electron micrograph of the fluorinated solid oxide of Example 15.

Definitions

To more clearly define the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions apply to this disclosure. If a term is used in this disclosure but not specifically defined herein, the definition in the IUPAC Compendium of Chemical Terminology, 2nd Ed. (1997), may be applied, provided that that definition does not conflict with any other disclosure or definition applied herein, or render any claim to which that definition applies disabled or undefined. To the extent that any definition or usage provided by any document incorporated by reference herein conflicts with the definition or usage provided herein, the definition or usage provided herein shall govern.

Features of the subject matter are described herein such that, within particular aspects, a combination of different features may be envisioned. For each and every aspect and/or feature described herein, all combinations that do not adversely affect the designs, compositions, processes, or methods described herein are contemplated, with or without an explicit description of the particular combination. Furthermore, unless explicitly indicated otherwise, any aspect and/or feature described herein may be combined to describe inventive designs, compositions, processes, or methods that are consistent with the present disclosure.

Although compositions and methods/processes are described herein in terms of "comprising" various components or steps, the compositions and methods/processes may also "consist essentially of" or "consist of" the various components or steps, unless otherwise indicated. For example, a catalyst composition consistent with aspects of the present invention may comprise; alternatively, may consist essentially of; or alternatively, may consist of; a metallocene compound, a fluorinated solid oxide, and a cocatalyst.

The terms "a," "an," and "the" are intended to include plural alternatives, for example, at least one, unless otherwise specified. For example, the description "a metallocene compound" or "comonomer" is intended to encompass one, or mixtures or combinations of more than one, metallocene compound or comonomer, respectively, unless otherwise specified.

In general, groups of elements are indicated using the numbering scheme given in the version of the periodic table of the elements published in Chemical and Engineering News, 63(5), 27, 1985. In some cases, a group of elements may be indicated by using a common name assigned to the group; for example, alkali metals for Group 1 elements, alkaline earth metals for Group 2 elements, transition metals for Group 3-12 elements, and halogens or halides for Group 17 elements.

For any particular compound discussed herein, the general name or structure presented also encompasses all structural isomers, conformational isomers, and stereoisomers that may arise from a particular set of substituents, unless otherwise indicated. Thus, a general reference to a compound includes all structural isomers unless explicitly indicated otherwise; for example, a general reference to pentane includes n-pentane, 2-methylbutane, and 2,2-dimethylpropane, while a general reference to a butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Additionally, reference to a general name or structure encompasses all enantiomers, diastereomers, and other optical isomers, whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context permits or requires.

The term "polymer" is used herein generically to include homopolymers, copolymers, terpolymers, and the like of olefins, as well as alloys and blends thereof. The term "polymer" also includes impact, block, graft, random, and alternating copolymers. A copolymer is derived from one olefin monomer and one olefin comonomer, while a terpolymer is derived from one olefin monomer and two olefin comonomers. Accordingly, "polymer" encompasses copolymers and terpolymers derived from any olefin monomer and comonomer(s) described herein. Similarly, the scope of the term "polymerization" includes homopolymerization, copolymerization, and terpolymerization. Thus, an ethylene polymer includes ethylene homopolymers, ethylene copolymers (e.g., ethylene/α-olefin copolymers), ethylene terpolymers, and the like, as well as mixtures or blends thereof. Thus, an ethylene polymer encompasses the polymers often referred to in the art as LLDPE (linear low-density polyethylene) and HDPE (high-density polyethylene). As an example, an olefin copolymer, such as an ethylene copolymer, can be derived from ethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer and comonomer were ethylene and 1-hexene, respectively, the resulting polymer can be classified as an ethylene/1-hexene copolymer. The term "polymer" also includes all possible geometric configurations, unless otherwise indicated, and such configurations can include isotactic, syndiotactic, and random symmetries. In addition, the “polymers” described herein (e.g., ethylene polymers) may also be referred to as “polymer compositions.”

The term "cocatalyst" is used generally herein to refer to compounds, such as aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like, which may constitute a component of a catalyst composition, when used, for example, in addition to a fluorinated solid oxide. The term "cocatalyst" is used without regard to the actual function of the compound or any chemical mechanism by which the compound may operate.

The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like, are independent of the actual product or composition resulting from the contact or reaction of the initial components of the disclosed or claimed catalyst composition/mixture/system, the nature of the active catalytic site, or the fate of the cocatalyst, metallocene compound, or fluorinated solid oxide after combining these components. Thus, the terms "catalyst composition," "catalyst mixture," "catalyst system," and the like, encompass the initial starting components of the composition as well as any product(s) that may result from contacting these initial starting components, and this includes both heterogeneous and homogeneous catalyst systems or compositions. The terms "catalyst composition," "catalyst mixture," "catalyst system," and the like, may be used interchangeably throughout this disclosure.

The term "contacting" is used herein to refer to materials or components that may be combined, mixed, suspended, dissolved, immersed, reacted, treated, sprayed, impregnated, blended, or otherwise brought into contact or combined in any other manner or by any suitable method. The materials or components may be contacted or combined with each other in any order, in any manner, and for any period of time, unless otherwise specified.

Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, typical methods, devices, and materials are described herein.

Various types of ranges are described herein. When a range of any type is disclosed or claimed, it is intended to individually disclose or claim each possible number that such a range could reasonably encompass, including the endpoints of the range, as well as any subranges and combinations of subranges that it encompasses. As a representative example, the pH of an aqueous mixture may lie within certain ranges in various aspects of this invention. By a disclosure that the pH may be in a range of about 4 to about 8, the intention is to recite that the pH may be any value within the range, and may, for example, be equal to about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, or about 8. Furthermore, the pH may be within any range from about 4 to about 8 (e.g., from about 4 to about 7.5), and this also includes any combination of ranges between about 4 and about 8 (e.g., the pH may be in a range from about 4.2 to about 6.8, or from about 4.5 to about 6.5). Furthermore, in all cases where “about” a particular value is disclosed, that value itself is disclosed. Thus, the disclosure of a pH range of about 4 to about 8 also discloses a pH range of 4 to 8 (e.g., 4 to 7.5), and this also includes any combination of ranges between 4 and 8 (e.g., the pH may be in a range of 4.2 to 6.8, or 4.5 to 6.5). Likewise, all other ranges disclosed herein should be construed similarly to this example.

The term "about" means that quantities, sizes, formulations, parameters, and other amounts and characteristics are not and need not be exact, but may be approximate or even greater or less, as desired, reflecting tolerances, conversion factors, rounding, measurement errors, and the like, and other factors known to those skilled in the art. In general, a quantity, size, formulation, parameter, or other amount or characteristic is "approximately" or "about," whether or not expressly stated to be so. The term "about" also encompasses quantities that differ due to different equilibrium conditions for a composition obtained from a particular initial mixture. Whether or not modified by the term "about," the claims include equivalents of the quantities. The term "about" may mean within 10% of the reported numerical value, preferably within 5% of the reported numerical value.

Detailed description

The present disclosure generally relates to fluorinated solid oxides, methods for preparing the fluorinated solid oxides, catalyst compositions employing the fluorinated solid oxides, methods for using the catalyst compositions to polymerize olefins, polymer resins produced using such catalyst compositions, and articles produced using these polymer resins.

Commercially produced fluorinated solid oxides, such as fluorinated silica-coated alumina, are typically prepared by immersing the solid oxide in a strongly acidic HF (or hydrofluoric acid) solution and allowing the fluorine sufficient time to permeate and react with the solid oxide. This process typically takes 12 hours before spray drying. Otherwise, if the reaction is incomplete, HF vapors may be released to the atmosphere. The neutralized slurry is then spray dried to produce very fine fluorinated solid oxide particles, generally with an average d50 particle size of less than 40 microns and, in some cases, less than 35 microns. Furthermore, due to fluorine emissions and safety considerations, this method of producing fluorinated solid oxides is not practiced in the United States.

The processes described herein for preparing fluorinated solid oxides offer several advantages. In one process, the acidic fluorine compound reacts with an inorganic base such that the resulting fluorine-containing aqueous mixture does not emit potentially hazardous hydrogen fluoride fumes into the atmosphere during spray drying. Furthermore, by increasing the pH of the aqueous mixture to a relatively neutral pH (>4.0), not only is the potential for hydrogen fluoride emissions eliminated prior to spray drying, but the corrosivity of the fluorine-containing aqueous mixture is also significantly reduced. In addition, the time required to neutralize the acid is significantly reduced, resulting in a more cost-effective process. Furthermore, fluorinated solid oxides with an average particle size d50 of greater than 40 microns, and in some cases, greater than 50 microns, can be readily produced.

In another process, the acidic fluorine compound is initially brought into contact with the solid oxide, but an inorganic base is then added to raise the pH to a relatively neutral pH. Therefore, as mentioned above, potentially hazardous hydrogen fluoride fumes are not emitted into the atmosphere during spray drying, and the corrosiveness of the fluorinated solid oxide to spray drying and other equipment is also significantly reduced.

Another potential benefit of the processes described, although not a requirement, is that the inorganic base can also be selected to increase the overall catalytic activity of the fluorinated solid oxide, such as by the addition of zinc or other suitable metal.

Solid fluorinated oxides

Various processes for producing a fluorinated solid oxide are described and disclosed herein. A first process for producing the fluorinated solid oxide may comprise (or consist essentially of, or consist of) (a) contacting a fluorine-containing acidic compound and an inorganic base to produce an aqueous mixture having a pH of at least about 4, and (b) contacting a solid oxide with the aqueous mixture to produce the fluorinated solid oxide. A second process for producing a fluorinated solid oxide may comprise (or consist essentially of, or consist of) (A) contacting a fluorine-containing acidic compound with a solid oxide to produce a mixture; and (B) contacting the mixture with an inorganic base to produce the fluorinated solid oxide at a pH of at least about 4.

Generally, the characteristics of any of the processes disclosed herein (e.g., the fluorine-containing acid compound, the inorganic base, the pH, the solid oxide, and the conditions under which the steps are carried out, among others) are independently described herein, and these characteristics may be combined in any combination to further describe the disclosed processes. In addition, other process steps may be carried out before, during, and/or after any of the listed steps in the disclosed processes, unless otherwise indicated. In addition, fluorinated solid oxides (also referred to as chemically treated solid oxides or activator support) produced according to the disclosed processes are within the scope of this disclosure and are covered herein.

Referring now to step (a) of the first process, a fluorine-containing acid compound and an inorganic base may be contacted to produce an aqueous mixture having a pH of at least about 4. The order in which the components are combined in step (a) to produce the aqueous mixture is not particularly limited. In one aspect, for example, the fluorine-containing acid compound may be contacted first with water and then with the inorganic base to produce the aqueous mixture, while in another aspect, the inorganic base may be contacted first with water and then with the fluorine-containing acid compound to produce the aqueous mixture.

Any suitable fluorine-containing acid compound may be used in step (a). Illustrative and non-limiting examples of the fluorine-containing acid compound include hydrogen fluoride (HF), ammonium bifluoride (NH4HF2), triflic acid (CF3SO3H), tetrafluoroboric acid (HBF4), hexafluorosilicic acid (H2SiF6), hexafluorophosphoric acid (HPF6), and the like. Combinations of two or more fluorine-containing acid compounds may be used to produce the aqueous mixture. In one aspect, the fluorine-containing acid compound may comprise (or consist essentially of, or consist of) hydrogen fluoride (HF), ammonium bifluoride (NH4HF2), triflic acid (CF3SO3H), tetrafluoroboric acid (HBF4), hexafluorosilicic acid (H2SiF6), hexafluorophosphoric acid (HPFa), or any combination thereof. In another aspect, the fluorine-containing acid compound may comprise (or consist essentially of, or consist of) hydrogen fluoride (HF); alternatively, ammonium bifluoride (NH4HF2); alternatively, triflic acid (CF3SO3H); alternatively, tetrafluoroboric acid (HBF4); alternatively, hexafluorosilicic acid (H2SiFa); or alternatively, hexafluorophosphoric acid (HPFa). In yet another aspect, the fluorine-containing acid compound may comprise tetrafluoroboric acid (HBF4), hexafluorosilicic acid (H2SiFa), or both.

Likewise, various inorganic bases can be used, and the inorganic bases typically contain a metal. For example, the inorganic base may contain Zn, Al, Fe, Mn, Ca, Mg, or combinations thereof (a zinc-containing inorganic base, an aluminum-containing inorganic base, an iron-containing inorganic base, a manganese-containing inorganic base, a calcium-containing inorganic base, a magnesium-containing inorganic base, or combinations thereof). Therefore, representative examples of inorganic bases that can be used in the described processes may include, but are not limited to, ZnO, Zn(OH)2, ZnCO3, Al(OH)3, Al2O3, AlOOH, Fe2O3, Fe(OH)3, Fe(OH)2, MnO2, Mn(OH)2, Ca(OH)2, CaCO3, Mg(OH)2, MgCO3, and the like. Combinations of two or more inorganic bases may be used to produce the aqueous mixture. In accordance with one aspect of this invention, the inorganic base may comprise ZnO, Zn(OH)2, and/or ZnCO3, while in another aspect, the inorganic base may comprise Al(OH)3, AhO3, and/or AlOOH, and in another aspect, the inorganic base may comprise Fe2O3, Fe(OH)3, and/or Fe(OH)2, and in another aspect, the inorganic base may comprise MnO2 and/or Mn(OH)2, and in yet another aspect, the inorganic base may comprise Ca(OH)2 and/or CaCO3, and in yet another aspect, the inorganic base may comprise Mg(OH)2 and/or MgCO3.

The fluorine-containing acid compound and the inorganic base can be combined to produce an aqueous mixture having a pH of at least about 4. Although not limited thereto, the pH can often be generally neutral, and can typically fall within a range of about 4 to about 8, such as, about 4 to about 7.5, about 4 to about 6, about 4 to about 5.5, about 4 to about 5, about 4.2 to about 7.5, about 4.2 to about 6.8, about 4.2 to about 5.5, about 4.5 to about 7.5, about 4.5 to about 6.5, about 5 to about 8, about 5 to about 7, or about 5 to about 6.

The relative number of acid equivalents of the fluorine-containing acid compound to the number of base equivalents of the inorganic base combined in step (a) can be selected so as to maintain a pH of at least about 4. Depending upon the particular fluorine-containing acid compound and inorganic base used, among other factors, the acid:base equivalent ratio (fluorine-containing acid compound to inorganic base) generally ranges from about 1.3:1 to about 1:3. Thus, in one aspect of this invention, the acid:base equivalent ratio can be in a range of from about 1.2:1 to about 1:2, and in another aspect, the ratio can be in a range of from about 1:1 to about 1:2, and in yet another aspect, the ratio can be in a range of from about 1:1.1 to about 1:1.8. As an example, 1 mole of Zn(OH)2 (or ZnO or ZnCO3) contains 2 equivalents of base, while 1 mole of HF (or HBF4) contains 1 equivalent of acid.

The respective molar ratio of F to the number of base equivalents of the inorganic base in the aqueous mixture is not particularly limited. Generally, the ratio can be found in the range of about 0.5:1 to about 8:1, about 0.8:1 to about 7:1, or about 1:1 to about 6:1.

Furthermore, depending on the pH and the particular fluorine-containing acid compound and inorganic base used, among other factors, the aqueous mixture may be a solution, or the aqueous mixture may be a suspension (e.g., with visible precipitation). Step (a) and step (b) of the process may be carried out in any suitable vessel, such as a stirred tank.

Step (a) of the process can be carried out at a variety of temperatures and time periods. For example, the fluorine-containing acid compound and the inorganic base can be combined to produce the aqueous mixture having a pH of at least about 4 at a temperature in a range of about 10°C to about 60°C; alternatively, from about 10°C to about 40°C; alternatively, from about 10°C to about 30°C; alternatively, from about 15°C to about 45°C; alternatively, from about 15°C to about 35°C; alternatively, from about 20°C to about 40°C; or alternatively, from about 20°C to about 30°C. In these and other respects, these temperature ranges are also intended to encompass circumstances where step (a) is carried out at a number of different temperatures, rather than at a single fixed temperature, which falls within the respective ranges, where at least one temperature falls within the ranges cited. Generally, ambient temperatures are conveniently used, and high temperatures are typically avoided to prevent the release of gaseous fluorine compounds.

The duration of step (a) is not limited to any particular period of time, so long as the fluorine-containing acid compound and the inorganic base have been mixed sufficiently to result in the aqueous mixture having a pH of at least about 4. Generally, however, step (a) may be carried out in a period of time that may be in a range of about 30 seconds to about 8 hours, such as, for example, about 1 minute to about 2 hours, about 1 minute to about 30 minutes, about 5 minutes to about 4 hours, about 5 minutes to about 15 hours, and the like.

Turning now to step (b) of the first process, the aqueous mixture is contacted with a solid oxide to produce the fluorinated solid oxide. Step (b) of the first process can be carried out at a variety of temperatures and time periods, such as, but not limited to, those described herein for step (a). Non-limiting examples of suitable fluorinated solid oxides are disclosed in, for example, U.S. Patent Nos. 7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973, 8,703,886, and 9023959.

The fluorinated solid oxide may contain any suitable solid oxide, such as a solid oxide containing a Lewis acid metal ion. The solid oxide may encompass oxide materials, such as alumina, "mixed oxides" thereof, such as silica-alumina, coatings of one oxide on another, and combinations and mixtures thereof. Mixed oxides such as silica-alumina may be single or multiple chemical phases with more than one metal combining with oxygen to form the solid oxide. Examples of mixed oxides that may be used to form an activator support, individually or in combination, may include, but are not limited to, silica-alumina, silica-titania, silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate, aluminaboria, silica-boria, aluminophosphate-silica, titania-zirconia, and the like. The solid oxide used herein also encompasses oxide materials, such as silica-coated alumina, as described in U.S. Patent No. 7,884,163 (e.g., Sasol Siral® 28, Sasol Siral® 40, etc.).

In one aspect, the solid oxide may comprise alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, any mixed oxides thereof, or any combination thereof. In another aspect, the solid oxide may comprise alumina, silica-alumina, silica-coated alumina, aluminum phosphate, aluminophosphate, heteropolytungstate, titania, zirconia, silica-zirconia, magnesia, or boria, as well as any mixed oxides thereof, or any mixture thereof. In another aspect, the solid oxide may comprise alumina, titania, zirconia, magnesia, boria, any mixed oxides thereof, or any mixture thereof, while in another aspect, the solid oxide may comprise silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-boria, or any combination thereof. In yet another aspect, the solid oxide may comprise alumina, titania, zirconia, magnesia, boria, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, alumina-boria, and the like, or any combination thereof. In yet another aspect, the solid oxide may comprise alumina, silica-alumina, silica-coated alumina, or any mixture thereof; alternatively, alumina; alternatively, silica-alumina; or alternatively, silica-coated alumina.

The silica-alumina or silica-coated alumina solid oxide materials that may be used may have a silica content of about 5 to about 95% by weight. In one aspect, the silica content of these solid oxides may be from about 10 to about 80%, or from about 20% to about 70%, of silica by weight. In another aspect, such materials may have silica contents ranging from about 15% to about 60%, from about 25% to about 50% by weight, or from about 25% by weight to about 45%, of silica by weight. The solid oxides contemplated herein may have any suitable surface area, pore volume, and particle size, as would be recognized by those skilled in the art.

In one aspect, the fluorinated solid oxide may comprise (or consist essentially of, or consist of) fluorinated alumina, fluorinated titania, fluorinated zirconia, fluorinated magnesia, fluorinated boria, fluorinated silica-alumina, fluorinated silica-coated alumina, fluorinated silica-titania, fluorinated silica-zirconia, fluorinated alumina-boria, and the like, as well as any mixture or combination thereof. In another aspect, the fluorinated solid oxide may comprise fluorinated alumina, fluorinated silica-alumina, fluorinated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, and the like, as well as any mixture or combination thereof. In yet another aspect, the fluorinated solid oxide may comprise fluorinated alumina; alternatively, fluorinated titania; alternatively, fluorinated zirconia; alternatively fluorinated magnesia; alternatively fluorinated boria; alternatively fluorinated silica-alumina; alternatively fluorinated silica-coated alumina; alternatively fluorinated silica-titania; alternatively fluorinated silica-zirconia; or alternatively fluorinated alumina-boria.

While not limited thereto, the fluorinated solid oxide may generally contain from about 0.5 to about 15% by weight of F, based on the weight of the fluorinated solid oxide (on a dry basis, excluding water). In particular aspects provided herein, the fluorinated solid oxide may contain from about 1 to about 12% by weight, from about 1 to about 8% by weight, from about 2 to about 15% by weight, from about 2 to about 9% by weight, from about 2 to about 7% by weight, from about 3 to about 12% by weight, or from about 3 to about 7% by weight, based on the total weight of the fluorinated solid oxide.

If the fluorine-containing compound includes boron, such as HBF4, then the fluorinated solid oxide may often contain from about 0.2 to about 1.2% by weight B, and in some aspects, from about 0.3 to about 1% by weight B, or from about 0.4 to about 0.9% by weight B, based on the total weight of the fluorinated solid oxide (on a dry basis, excluding water).

Likewise, but not limited thereto, the fluorinated solid oxide may also contain from about 0.5% to about 15% by weight of the inorganic base metal (e.g., Zn, Fe, Mn, Ca, and Mg, either individually or in any combination), based on the weight of the fluorinated solid oxide (on a dry basis, excluding water). For example, as a result of using ZnO as the inorganic base, the fluorinated solid oxide may contain from about 0.5 to about 15% by weight of Zn. Likewise, if Mg(OH)2 is the inorganic base, the fluorinated solid oxide may contain from about 0.5 to about 15% by weight of Mg. If desired, a mixture of inorganic bases may be used, such as, a mixture of ZnO and MgCO3; In such cases, the fluorinated solid oxide contains a total Zn and Mg content that is within a range of from about 0.5 to about 15% by weight. In particular aspects provided herein, the fluorinated solid oxide may contain from about 0.5 to about 5% by weight, from about 1 to about 12% by weight, from about 1 to about 10% by weight, from about 1 to about 8% by weight, from about 1 to about 5% by weight, from about 1 to about 3.5% by weight, from about 1.5 to about 8% by weight, or from about 1.5 to about 5% by weight, of the inorganic base metal, based on the total weight of the fluorinated solid oxide.

These respective amounts of fluorine, boron (if present) and metal (e.g., Zn, Fe, Mn, Ca and Mg, either individually or in any combination) in the fluorinated solid oxide may be present after drying and before calcining the fluorinated solid oxide, as well as after calcining the fluorinated solid oxide.

Prior to calcination, the fluorinated solid oxide may also be characterized by the presence of a reaction product of the fluorine-containing acid compound and the inorganic base. In one aspect, for example, when the fluorine-containing acid compound is tetrafluoroboric acid (HBF4) and the inorganic base is a zinc-containing base such as ZnO, then the fluorinated solid oxide may comprise a solid oxide and from about 1 to about 18% by weight (or from about 3 to about 13% by weight, or from about 4 to about 10% by weight, or from about 5 to about 9% by weight) of Zn(BF4). In another aspect, when the fluorine-containing acid compound is hexafluorosilicic acid (H2SiF6) and the inorganic base is a zinc-containing base, such as, ZnO, then the fluorinated solid oxide may comprise a solid oxide and from about 1 to about 18% by weight (or from about 3 to about 13% by weight, or from about 4 to about 10% by weight, or from about 5 to about 9% by weight) of ZnSiF6.

The fluorinated solid oxide may have any suitable total pore volume, BET surface area, and particle size. As a non-limiting example, the fluorinated solid oxide may have a total pore volume in a range of about 0.5 to about 2.5 mL/g in one aspect, about 0.5 to about 2 mL/g in another aspect, and about 0.7 to about 1.5 mL/g in yet another aspect. The BET surface area of the fluorinated solid oxide is not particularly limited and may range from about 150 to about 700 m/g in one aspect, from about 200 to about 700 m/g in another aspect, and from about 250 to about 500 m/g in yet another aspect. Similarly, the average particle size (d50) of the fluorinated solid oxide is not particularly limited and may vary from about 10 to about 500 microns in one aspect, from about 25 to about 200 microns in another aspect, and from about 20 to about 100 microns in yet another aspect.

Optionally, an additional metal or metals can be impregnated onto the fluorinated solid oxide. While not limited to this, this can be achieved by contacting a metal-containing compound with the fluorine-containing acidic compound and the inorganic base. The metal-containing compound can include the metal and an organic group (e.g., acetate), or the metal-containing compound can be inorganic (e.g., nitrate). Examples can include, but are not limited to, zinc, nickel, cobalt, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium, and the like, or combinations thereof. The metal in the inorganic base and the metal in the metal-containing compound can be the same (e.g., zinc) or different (e.g., zinc and cobalt). In one aspect, the metal-containing compound can comprise an organozinc compound, such as zinc acetate and/or zinc formate.

When an additional metal is impregnated, the fluorinated solid oxide may contain any suitable amount of the metal of the metal-containing compound, often ranging from about 0.5 to about 10% by weight of the metal of the metal-containing compound, based on the weight of the fluorinated solid oxide (on a dry basis, excluding water). In particular aspects provided herein, the fluorinated solid oxide may contain from about 0.5 to about 5% by weight, from about 1 to about 12% by weight, from about 1 to about 10% by weight, from about 1 to about 8% by weight, from about 1 to about 4% by weight, from about 1.5 to about 8% by weight, or from about 1.5 to about 5% by weight, of the metal of the metal-containing compound, based on the total weight of the fluorinated solid oxide.

Referring now to the second process for producing a fluorinated solid oxide, which may comprise (A) contacting a fluorine-containing acidic compound with a solid oxide to produce a mixture, and (B) contacting the mixture with an inorganic base to produce the fluorinated solid oxide at a pH of at least about 4. In the second process, the selections for the fluorine-containing acidic compound, the solid oxide, the inorganic base, and the fluorinated solid oxide are the same as those described herein for the first process. Likewise, the pH conditions, acid-base equivalents, molar ratios of F to base equivalents, and other features described herein for the first process are also applicable to the second process. Additionally, step (A) and step (B) of the second process may be carried out at a variety of temperatures and time periods, such as, but not limited to, those described herein for step (a) of the first process.

The first process and the second process may further comprise a step of drying the fluorinated solid oxide, and any suitable technique or any technique disclosed herein may be used. For example, excess liquid may be removed from the fluorinated solid oxide (e.g., by draining, filtering, etc.) and the wet fluorinated solid oxide may be subjected to a wide range of drying times, drying temperatures, and drying pressures. For example, the drying time may range from about 15 minutes to about 48 hours, from about 30 minutes to about 24 hours, or from about 1 to about 12 hours, and the drying temperature may range from about 50°C to about 300°C, from about 95°C to about 300°C, or from about 100°C to about 275°C. The drying pressure may be at or near atmospheric pressure, but in many cases, the drying step may be performed under vacuum conditions at any suitable subatmospheric pressure, such as, less than 100 torr (13.3 kPa), less than 50 (6.67 kPa) torr, or less than 10 torr (1.33 kPa).

Various types of drying devices can be used for the drying step, such as, but not limited to, tray dryers, rotary dryers, fluidized-bed dryers, and spray dryers. Likewise, the flow of the drying medium (gas flow) relative to the fluorinated solid oxide is not particularly limited and includes concurrent flow, countercurrent flow, and continuous flow (e.g., as in a fluidized bed).

In some aspects of this invention, the drying step may comprise spray drying the solid fluorinated oxide. Generally, spray drying may be used to transform the wet solid fluorinated oxide (e.g., a slurry of the solid fluorinated oxide in water) into a dry particulate or powder form by spraying a feed stream containing the wet solid fluorinated oxide into a device containing a heated drying gas (generally air), wherein residual water evaporates from the solid fluorinated oxide.

In the spray drying process, the feed stream may be sprayed into a drying chamber in the form of droplets and come into contact with a large volume of hot gas, which directly contacts the wet solid oxide. Typical inlet gas temperatures range from 95°C to about 800°C, or from about 100°C to about 500°C, but are not limited to these. The gas flow relative to the solid flow in the spray dryer may be cocurrent flow, countercurrent flow, or mixed flow. After drying, the gas stream and the dried fluorinated solid oxide are separated. If necessary, fine particles may be removed in filter collectors or cyclones. The dried fluorinated solid oxide may be in the form of free-flowing solid particles.

The initial feed to the spray dryer can undergo an atomization process, which may employ, for example, a high-pressure nozzle, a two-fluid nozzle, or a high-speed centrifugal disc. High-pressure nozzles produce atomization by forcing the solid-support slurry under high pressure through a small nozzle orifice, the size of which can depend on the desired pressure and the particle size of the solids in the slurry, among other factors. During long-term operation, nozzle orifice wear and clogging can occur; therefore, regular maintenance can be beneficial to ensure adequate atomization. Two-fluid nozzles have the advantage of a relatively low operating pressure and can often be used when the feed stream is a thick or high-solids slurry, which does not perform well in high-pressure nozzle systems. The atomizing fluid can be steam or air.

High-speed centrifugal discs atomize the fluorinated solid oxide suspension by bringing it into contact with a rapidly rotating disc. Disc diameter and speed (e.g., 3000 rpm and higher) can be varied to produce a droplet size suitable for drying. The advantage is that disc atomization is not subject to wear or clogging as with nozzle systems. Disc rotation can be driven by any suitable motor or technique.

Regardless of the atomization process, the spray drying process can be configured to maintain the spherical nature of the fluorinated solid oxide. The average particle size of the solid material can be maintained in many cases, and generally, the average particle size depends on the atomization process, the solids content of the solid oxide feed stream, the feed stream viscosity, and the feed rate, among other factors. Likewise, the bulk density of the dried fluorinated solid oxide can be controlled based on the spray dryer operating conditions, such as droplet size, inlet gas temperature, and air turbulence, among other factors.

Mixing of the gas stream (e.g., air) and the droplet in the drying chamber can be achieved, for example, by using a simultaneous flow of gas and solids (e.g., horizontal or vertical spray dryers), or by using a countercurrent flow of gas and solids. In the latter case, the upward airflow can carry fine particles to the top of the chamber for easy removal. Mixed-flow spray dryers combine countercurrent and concurrent drying, with complex flow patterns and high turbulence for efficient heat and mass transfer.

One advantage of spray drying can be the short contact time of the fluorinated solid oxide at elevated temperatures in the drying chamber. This way, in addition to the average particle size, the spray drying process can be configured to produce dry fluorinated solid oxides with surface areas and pore volumes comparable to the starting material (i.e., before spray drying).

Optionally, after drying, the fluorinated solid oxide can be calcined (to produce a calcined fluorinated solid oxide), which can be done at a variety of temperatures and time periods. Typical maximum calcination temperatures are typically in the range of about 400°C to about 1000°C, such as, for example, about 400°C to about 900°C, about 500°C to about 800°C, or about 550°C to about 700°C. In these and other aspects, these temperature ranges are also intended to encompass circumstances where the calcination step is carried out at a plurality of different temperatures (e.g., an initial calcination temperature, a maximum calcination temperature), rather than at a single fixed temperature, that fall within the respective ranges.

The duration of the calcination step is not limited to any particular time period. Thus, the calcination step may be carried out, for example, in a time period ranging from as little as 30-45 minutes to as much as 36-48 hours or more. The appropriate calcination time may depend, for example, on the initial/maximum calcination temperature, among other variables. Generally, however, the calcination step may be carried out in a time period that may be in a range of about 30 minutes to about 48 hours, such as, for example, from about 1 hour to about 24 hours, from about 1 hour to about 12 hours, from about 2 hours to about 12 hours, or from about 2 hours to about 8 hours.

The calcining step may be carried out in a calcining gas stream comprising (or consisting essentially of, or consisting of) an inert gas (e.g., nitrogen), oxygen, air, or any mixture or combination thereof. In some aspects, the calcining gas stream may comprise air, while in other aspects, the calcining gas stream may comprise a mixture of air and nitrogen. However, in certain aspects, the calcining gas stream may be an inert gas, such as nitrogen and/or argon.

The calcination step can be performed using any suitable technique and equipment, either batchwise or continuously. For example, the calcination step can be performed in a ribbon calciner or, alternatively, in a rotary calciner. In some aspects, the calcination step can be performed in a batch or continuous calcination vessel comprising a fluidized bed. As those skilled in the art would recognize, other suitable techniques and equipment can be employed for the calcination step, and such techniques and equipment are covered herein.

Catalyst compositions

In some aspects, the present invention employs catalyst compositions comprising a metallocene compound and a fluorinated solid oxide activator. These catalyst compositions can be used to produce polyolefins—homopolymers, copolymers, and the like—for a variety of end-use applications. In aspects of the present invention, it is contemplated that the catalyst composition may contain more than one metallocene compound (two or more metallocene compounds). In addition, more than one fluorinated solid oxide activator may also be used.

Generally, the catalyst compositions of the present disclosure comprise a metallocene compound and a fluorinated solid oxide. Optionally, such catalyst compositions may further comprise one or more than one cocatalyst compound(s) (suitable cocatalysts, such as organoaluminum compounds, are also discussed herein). Thus, the catalyst composition may comprise a metallocene compound, a fluorinated solid oxide, and an organoaluminum compound. For example, the fluorinated solid oxide may comprise (or consist essentially of, or consist of) fluorinated alumina, fluorinated silica-alumina, fluorinated silica-zirconia, fluorinated silica-titania, fluorinated silica-coated alumina, and the like or combinations thereof. Additionally, the organoaluminum compound may comprise (or consist essentially of, or consist of) trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like, or combinations thereof. Accordingly, a catalyst composition according to aspects of the invention may comprise (or consist essentially of, or consist of) a metallocene compound; fluorinated alumina (or fluorinated silica-alumina, or fluorinated silica-coated alumina); and triethylaluminum (or triisobutylaluminum).

In another aspect, a catalyst composition is provided comprising a metallocene compound, a fluorinated solid oxide, and an organoaluminum compound, wherein this catalyst composition is substantially free of aluminoxanes, organoboron or organoborate compounds, ionizing ionic compounds, or combinations thereof; alternatively, substantially free of aluminoxanes; alternatively, substantially free of organoboron or organoborate compounds; or alternatively, substantially free of ionizing ionic compounds. In these aspects, the catalyst composition has catalyst activity, discussed below, in the absence of these additional materials. For example, a catalyst composition can consist essentially of a metallocene compound, a fluorinated solid oxide, and an organoaluminum compound, where there are no other materials present in the catalyst composition that increase/decrease the activity of the catalyst composition by more than about 10% of the catalyst activity of the catalyst composition in the absence of such materials.

However, such activators/cocatalysts may be employed in other aspects. For example, a catalyst composition comprising a metallocene complex and a fluorinated solid oxide may further comprise a cocatalyst. Suitable cocatalysts in this aspect may include, but are not limited to, aluminoxane compounds, organoboron or organoborate compounds, ionizing ionic compounds, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, and the like, or any combination thereof; or alternatively, organoaluminum compounds, organozinc compounds, organomagnesium compounds, organolithium compounds, or any combination thereof. More than one cocatalyst may be present in the catalyst composition.

Any suitable metallocene compound can be used in the catalyst composition. For example, the metallocene compound of the catalyst systems provided herein, in some aspects, comprise an unbridged metallocene; alternatively, an unbridged zirconium- or hafnium-based metallocene compound; alternatively, an unbridged zirconium- or hafnium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl group and one indenyl group; alternatively, an unbridged zirconium-based metallocene compound containing two cyclopentadienyl groups, two indenyl groups, or one cyclopentadienyl group and one indenyl group. These cyclopentadienyl groups and indenyl groups, independently, may be unsubstituted or may be substituted with any suitable substituent (one or more than one). Illustrative and non-limiting examples of non-bridged metallocene compounds (e.g., with zirconium or hafnium) that can be employed in catalyst systems consistent with aspects of the present invention are described in U.S. Patent Nos. 7,199,073, 7,226,886, 7,312,283, and 7,619,047.

In other aspects, the metallocene compound of the catalyst compositions provided herein may comprise a bridged metallocene compound, for example, with titanium, zirconium, or hafnium, such as, a bridged zirconium- or hafnium-based metallocene compound with a fluorenyl group, or alternatively, a bridged zirconium- or hafnium-based metallocene compound with a cyclopentadienyl group and a fluorenyl group. These cyclopentadienyl groups and fluorenyl groups, independently, may be unsubstituted or may be substituted with any suitable substituent (one or more than one).

For example, such bridged metallocenes may contain an alkenyl substituent (e.g., a terminal alkenyl) on the bridging group, on a cyclopentadienyl-type group (e.g., a cyclopentadienyl group or a fluorenyl group), or on both the bridging group and the cyclopentadienyl-type group. In other aspects, the metallocene catalyst compound may comprise a bridged zirconium- or hafnium-based metallocene compound having a fluorenyl group, and an aryl group on the bridging group; alternatively, a bridged zirconium- or hafnium-based metallocene compound having a cyclopentadienyl group and a fluorenyl group, and an aryl group on the bridging group; alternatively, a bridged zirconium- or hafnium-based metallocene compound having a fluorenyl group, and an aryl group on the bridging group; or alternatively, a bridged hafnium-based metallocene compound having a fluorenyl group, and an aryl group on the bridging group. In these and other embodiments, the aryl group of the bridging group may be a phenyl group. Optionally, these bridged metallocenes may contain an alkenyl substituent (e.g., a terminal alkenyl) on the bridging group, on a cyclopentadienyl-type group, or on both the bridging group and the cyclopentadienyl group. Illustrative and non-limiting examples of bridged metallocene compounds (e.g., with zirconium or hafnium) that can be employed in catalyst systems compatible with aspects of the present invention are described in U.S. Patent Nos. 7,026,494, 7,041,617, 7,226,886, 7,312,283, 7,517,939, and 7,619,047.

The catalyst composition may be produced in any manner, such as by contacting the metallocene compound, the fluorinated solid oxide, and the cocatalyst (if used) in any order.

In general, the weight ratio of cocatalyst (e.g., an organoaluminum compound) to fluorinated solid oxide may be in a range of about 10:1 to about 1:1000. If more than one cocatalyst compound and/or more than one fluorinated solid oxide are employed, this ratio is based on the total weight of each respective component. In another aspect, the weight ratio of cocatalyst to fluorinated solid oxide may be in a range of about 3:1 to about 1:500, or about 1:10 to about 1:350.

In some aspects of this invention, the weight ratio of metallocene complex to activator (fluorinated solid oxide) may be in a range of about 1:1 to about 1:1,000,000. If more than one metallocene compound and/or more than one fluorinated solid oxide is employed, this ratio is based on the total weights of the respective components. In another aspect, this weight ratio may be in a range of about 1:5 to about 1:100,000, or from about 1:10 to about 1:10,000. However, in another aspect, the weight ratio of the metallocene to the fluorinated solid oxide may be in a range of about 1:20 to about 1:1,000.

The catalyst compositions of the present invention generally have a catalyst activity of greater than about 1,000 grams, greater than about 2,000 grams, greater than about 3,000 grams, greater than about 4,000 grams, etc., of ethylene polymer (homopolymer or copolymer, as the context requires) per gram of the solid fluorinated oxide per hour (abbreviated g/g/h). In another aspect, the catalyst activity may be greater than about 6,000, greater than about 8,000, or greater than about 10,000 g/g/h and may often be in the range of up to 13,000-18,000 g/g/h. These activities are measured under slurry polymerization conditions, with a triisobutylaluminum cocatalyst, using isobutane as the diluent, at a polymerization temperature of 95 °C and a reactor pressure of 2.76 MPa (400 psig). In addition, an excess of metallocene compound (1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl) methane zirconium dichloride) may be used, and the fluorinated solid oxide may comprise, but is not limited to, fluorinated silica-coated alumina.

Coca-Colators

In certain aspects directed to catalyst compositions containing a cocatalyst and polymerization processes using a cocatalyst, the cocatalyst may comprise a metal hydrocarbyl compound, examples of which include non-halide metal hydrocarbyl compounds, metal hydrocarbyl halide compounds, non-halide metal alkyl compounds, metal alkyl halide compounds, etc. The hydrocarbyl group (or alkyl group) may be any hydrocarbyl (or alkyl) group described herein. Furthermore, in some aspects, the metal of the metal hydrocarbyl may be a Group 1, 2, 11, 12, 13, or 14 metal; alternatively, a Group 13 or 14 metal; or alternatively, a Group 13 metal. Thus, in some aspects, the metal of the metal hydrocarbyl (or non-halide metal hydrocarbyl or metal hydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron, aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum, or tin; alternatively, lithium, sodium, or potassium; alternatively, magnesium or calcium; alternatively, lithium; alternatively, sodium; alternatively, potassium; alternatively, magnesium; alternatively, calcium; alternatively, zinc; alternatively, boron; alternatively, aluminum; or alternatively, tin. In some aspects, the metal hydrocarbyl or metal alkyl, with or without a halide, may comprise a lithium hydrocarbyl or alkyl, a magnesium hydrocarbyl or alkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbyl or alkyl, or an aluminum hydrocarbyl or alkyl.

In particular aspects directed to catalyst compositions containing a cocatalyst and polymerization processes using a cocatalyst, the cocatalyst may comprise an aluminoxane compound (e.g., a supported aluminoxane), an organoboron or organoborate compound, an ionizing ionic compound, an organoaluminum compound, an organozinc compound, an organomagnesium compound, or an organolithium compound, and this includes any combinations of these materials. In one aspect, the cocatalyst may comprise an organoaluminum compound. In another aspect, the cocatalyst may comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, an organozinc compound, an organomagnesium compound, an organolithium compound, or any combination thereof. In yet another aspect, the cocatalyst may comprise an aluminoxane compound; alternatively, an organoboron or organoborate compound; alternatively, an ionizing ionic compound; alternatively, an organozinc compound; alternatively, an organomagnesium compound; or alternatively, an organolithium compound.

Specific non-limiting examples of suitable organoaluminum compounds may include trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminum chloride, and the like, or combinations thereof. Representative and non-limiting examples of aluminoxanes include methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane, sec-butylaluminoxane, isobutylaluminoxane, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane, neopentylaluminoxane, and the like, or any combination thereof. Representative and non-limiting examples of organoboron/organoborate compounds include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]borate, and the like, or mixtures thereof.

Examples of ionizing ionic compounds may include, but are not limited to, the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate, tri(n-butyl)ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate, N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-dimethylphenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate triphenylcarbenium, triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate, triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropylium tetrakis(ptolyl)borate, tetrakis(m-tolyl)tropylium borate, tetrakis(2,4-dimethylphenyl)tropylium borate, tropylium tetrakis(3,5-dimethylphenyl)borate, tropylium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropylium tetrakis(pentafluorophenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithium tetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate lithium, lithium tetrakis(2,4-dimethylphenyl)borate, lithium tetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodium tetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodium tetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodium tetrakis(2,4-dimethylphenyl)borate, sodium tetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassium tetrakis(pentafluorophenyl)borate, tetraphenylborate potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate, potassium tetrakis(2,4-dimethylphenyl)borate, potassium tetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithium tetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate, lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate, lithium tetrakis(2,4-dimethylphenyl)aluminate, lithium tetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate, sodium tetrakis(pentafluorophenyl)aluminate, sodium tetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate, sodium tetrakis(2,4-dimethylphenyl)aluminate, sodium tetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate, potassium tetrakis(pentafluorophenyl)aluminate, potassium tetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassium tetrakis(m-tolyl)aluminate, potassium tetrakis(2,4-dimethylphenyl)aluminate, potassium tetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate and the like, or combinations thereof.

Exemplary organozinc compounds that can be used as cocatalysts may include, but are not limited to, dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc, di(triethylsilyl)zinc, di(triisopropylsilyl)zinc, di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc, di(trimethylsilylmethyl)zinc and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds may include, but are not limited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, dineopentylmagnesium, di(trimethylsilylmethyl)magnesium, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesium bromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide, ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide, neopentylmagnesium, trimethylsilylmethylmagnesium iodide, methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesium ethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide, trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide, ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesium propoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesium propoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide, propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesium phenoxide, trimethylsilylmethylmagnesium phenoxide and the like, or any combinations thereof.

Likewise, exemplary organolithium compounds may include, but are not limited to, methyllithium, ethyllithium, propyllithium, butyllithium (e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium, phenyllithium, tolyllithium, xylyllithium, benzyllithium, (dimethylphenyl)methyllithium, allyllithium, and the like, or combinations thereof.

The cocatalysts that can be used in the catalyst compositions of this invention are not limited to the cocatalysts described above. Other suitable cocatalysts are well known to those skilled in the art, including, for example, those disclosed in U.S. Patent Nos. 3,242,099, 4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,599, 7,601,665, 7,884,163, 8,114,946, and 8,309,485.

Polymerization processes

The catalyst compositions can be used to polymerize olefins to form homopolymers, copolymers, terpolymers, and the like, and are discussed herein. One such process for polymerizing olefins in the presence of a catalyst composition of the present invention may comprise contacting the catalyst composition with an olefin monomer and, optionally, one or more olefin comonomers in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition may comprise a metallocene compound, a fluorinated solid oxide, and an optional cocatalyst. Metallocene complexes, fluorinated solid oxide activators, and cocatalysts are discussed herein. Therefore, aspects of this invention are directed to a process for polymerizing olefins in the presence of a catalyst composition, the process comprising contacting a catalyst composition with ethylene and optionally one or more olefin comonomers under polymerization conditions to produce an ethylene polymer. Furthermore, the present invention encompasses olefin polymerization processes comprising any of the processes for producing a fluorinated solid oxide disclosed herein (e.g., comprising (a) contacting a fluorine-containing acidic compound and an inorganic base to produce an aqueous mixture having a pH of at least about 4, and (b) contacting a solid oxide with the aqueous mixture to produce the fluorinated solid oxide; or comprising (A) contacting a fluorine-containing acidic compound with a solid oxide to produce a mixture, and (B) contacting the mixture with an inorganic base to produce the fluorinated solid oxide at a pH of at least about 4), contacting a metallocene compound, the fluorinated solid oxide, and an optional cocatalyst to form a catalyst composition, and contacting the catalyst composition with an olefin monomer and optionally one olefin comonomer (one or more) in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

The catalyst compositions are intended for any olefin polymerization method in which various types of reactor systems and polymerization reactors are used. The polymerization reactor system may include any polymerization reactor capable of polymerizing olefin monomers and comonomers (one or more comonomers) to produce homopolymers, copolymers, terpolymers, and the like. The various reactor types include those that may be mentioned as loop reactors, slurry reactors, gas-phase reactors, solution reactors, high-pressure reactors, tubular reactors, autoclave reactors, and the like, or combinations thereof. Suitable polymerization conditions are used for the various reactor types. Gas-phase reactors may comprise fluidized-bed reactors or horizontal phased reactors. Slurry reactors may comprise vertical or horizontal loops. High-pressure reactors may comprise autoclave or tubular reactors. Reactor types may include batch or continuous processes. Continuous processes may use intermittent or continuous product discharge. Processes may also include partial or complete direct recycling of unreacted monomer, unreacted comonomer, and/or diluent.

The polymerization reactor systems of the present invention may comprise one type of reactor in a system or multiple reactors of the same or different types (e.g., a single reactor, a dual reactor, more than two reactors). The production of polymers in multiple reactors may include several stages in at least two separate polymerization reactors interconnected by a transfer device that makes it possible to transfer the resulting polymers from the first polymerization reactor to the second reactor. The desired polymerization conditions in one of the reactors may be different from the operating conditions of the other reactor(s). Alternatively, the polymerization in multiple reactors may include manual transfer of polymer from one reactor to subsequent reactors for continuous polymerization. Multi-reactor systems may include any combination including, but not limited to, multiple loop reactors, multiple gas phase reactors, a combination of gas phase and loop reactors, multiple high pressure reactors, or a combination of loop and/or gas phase high pressure reactors. The multiple reactors may be operated in series, in parallel, or both. Accordingly, the present invention encompasses polymerization reactor systems comprising a single reactor, comprising two reactors, and comprising more than two reactors. The polymerization reactor system may comprise a slurry reactor, a gas phase reactor, a solution reactor, in certain aspects of this invention, as well as multi-reactor combinations thereof.

In one aspect, the polymerization reactor system may comprise at least one loop slurry reactor comprising vertical or horizontal loops. Monomer, diluent, catalyst, and comonomer may be continuously fed to a loop reactor, where polymerization occurs. Generally, continuous processes may comprise the continuous introduction of monomer/comonomer, a catalyst, and a diluent into a polymerization reactor and the continuous removal of a slurry from this reactor, comprising polymer particles and the diluent. The reactor effluent may be flashed to remove solid polymer from liquids comprising the diluent, monomer, and/or comonomer. Various technologies may be used for this separation step, including, but not limited to, flash evaporation, which may include any combination of heat addition and pressure reduction, separation by cyclonic action in a cyclone or hydrocyclone, or separation by centrifugation.

A typical suspension polymerization process (also known as a particulate process) is disclosed, for example, in U.S. Patent Nos. 3,248,179, 4,501,885, 5,565,175, 5,575,979, 6,239,235, 262,191, 6,833,415, and 8,822,608.

Suitable diluents used in slurry polymerization include, but are not limited to, the monomer being polymerized and hydrocarbons that are liquid under polymerization conditions. Examples of suitable diluents include, but are not limited to, hydrocarbons such as propane, cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, and n-hexane. Some loop polymerization reactions can be carried out under bulk conditions where no diluent is used, such as those that can be employed in the bulk polymerization of propylene to form polypropylene homopolymers.

In yet another aspect of this invention, the polymerization reactor system may comprise at least one gas phase reactor. Such systems may employ a continuous recycle stream containing one or more monomers continuously circulating through a fluidized bed in the presence of the catalyst, under polymerization conditions. A recycle stream may be withdrawn from the fluidized bed and recycled back to the reactor. Simultaneously, the polymer product may be withdrawn from the reactor and fresh or newly prepared monomer may be added to replace the polymerized monomer. Such gas phase reactors may comprise a multi-stage gas phase olefin polymerization process, wherein the olefins are polymerized in the gas phase in at least two separate gas phase polymerization zones while a catalyst-containing polymer formed in a first polymerization zone is supplied to a second polymerization zone. One type of gas phase reactor is disclosed in U.S. Patent Nos. 5,352,749, 4,588,790, 5,436,304, 7,531,606 and 7,598,327.

According to yet another aspect of the invention, a high-pressure polymerization reactor may comprise a tubular reactor or an autoclave reactor. Tubular reactors may have several zones where freshly prepared monomers, initiators, or catalysts are added. The monomer may be entrained in an inert gas stream and introduced into one zone of the reactor. The initiators, catalysts, and/or catalyst components may be entrained in a gas stream and introduced into another zone of the reactor. The gas streams may be intermixed for polymerization. Heat and pressure may be appropriately employed to obtain optimal polymerization reaction conditions.

In yet another aspect of the invention, the polymerization reactor system may comprise a solution polymerization reactor wherein the monomer (and comonomer, if used) are contacted with the catalyst composition by suitable agitation or other means. A carrier comprising an inert organic diluent or excess monomer may be employed. If desired, the monomer/comonomer may be contacted in the vapor phase with the catalytic reaction product, in the presence or absence of liquid material. The polymerization zone is maintained at temperatures and pressures that will result in the formation of a solution of the polymer in a reaction medium. Agitation may be employed to achieve improved temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. Suitable means are used to dissipate the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention may further comprise any combination of at least one feedstock feed system, at least one feed system for the catalyst or catalyst components, and/or at least one polymer recovery system. Reactor systems suitable for the present invention may further comprise systems for raw material purification, catalyst storage and preparation, extrusion, reactor cooling, polymer recovery, fractionation, recycling, storage, unloading, laboratory analysis, and process control.

Polymerization conditions that are controlled to achieve efficiency and to provide desired polymer properties may include temperature, pressure, and the concentrations of various reactants. The polymerization temperature may affect catalyst productivity, polymer molecular weight, and molecular weight distribution. A suitable polymerization temperature may be any temperature below the depolymerization temperature, according to the Gibbs free energy equation. Typically, this includes from about 35°C to about 280°C, for example, or from about 50°C to about 175°C, depending on the type of polymerization reactor(s). In some reactor systems, the polymerization temperature may generally fall within a range of from about 60°C to about 120°C, or from about 70°C to about 100°C. Various polymerization conditions may be held substantially constant, for example, for the production of a particular grade of olefin polymer.

Suitable pressures will also vary depending on the reactor and polymerization type. The pressure for liquid-phase polymerizations in a loop reactor is typically less than 6.9 MPa (1,000 psig). The pressure for gas-phase polymerization is usually about 1.4 MPa to 3.4 MPa (200 to 500 psig). High-pressure polymerization in tubular or autoclave reactors is generally carried out at about 138 to 517 MPa (20,000 to 75,000 psig). Polymerization reactors can also be operated in a supercritical region, which generally occurs at higher temperatures and pressures (e.g., above 92°C and 4.83 MPa (700 psig)). Operation above the critical point of a pressure/temperature diagram (supercritical phase) can offer advantages to the polymerization reaction process.

Aspects of this invention relate to olefin polymerization processes carried out in the absence of added hydrogen. An olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and, optionally, an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition may comprise a metallocene compound, a fluorinated solid oxide, and an optional cocatalyst, and wherein the polymerization process is carried out in the absence of added hydrogen (no hydrogen is added to the polymerization reactor system). As one of ordinary skill in the art would recognize, hydrogen can be generated in situ by catalyst compositions in various olefin polymerization processes, and the amount generated can vary depending on the specific catalyst composition and metallocene compound employed, the type of polymerization process used, the polymerization reaction conditions used, etc.

In other aspects, it may be desirable to carry out the polymerization process in the presence of a certain amount of added hydrogen. Accordingly, an olefin polymerization process of this invention may comprise contacting a catalyst composition with an olefin monomer and, optionally, an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition may comprise a metallocene compound, a fluorinated solid oxide, and an optional cocatalyst, and wherein the polymerization process is carried out in the presence of added hydrogen (hydrogen is added to the polymerization reactor system). For example, the ratio of hydrogen to olefin monomer in the polymerization process can be controlled, often by the ratio of hydrogen feed to olefin monomer entering the reactor. The ratio of hydrogen added to olefin monomer in the process can be controlled at a weight ratio falling within a range of about 25 ppm to about 1500 ppm, about 50 to about 1000 ppm, or about 100 ppm to about 750 ppm.

In some aspects of this invention, the feed or reactant ratio of hydrogen to olefin monomer can be maintained substantially constant during the polymerization cycle for a particular polymer grade. That is, the ratio of hydrogen:olefin monomer can be selected at a particular ratio within a range of about 5 ppm to about 1000 ppm or so, and maintained at the ratio within about +/- 25% during the polymerization cycle. For example, if the target ratio is 100 ppm, then maintaining the ratio of hydrogen:olefin monomer substantially constant would entail maintaining the feed ratio between about 75 ppm and about 125 ppm. Furthermore, the addition of comonomer(s) can be, and generally is, substantially constant throughout the polymerization cycle for a particular polymer grade.

However, in other aspects, it is contemplated that the monomer, comonomer(s), and/or hydrogen may be periodically pulsed into the reactor, for example, in a manner similar to that employed in U.S. Patent No. 5,739,220 and U.S. Patent Publication No. 2004/0059070.

The concentration of reactants entering the polymerization reactor system can be controlled to produce resins with specific physical and mechanical properties. The proposed end-use product to be formed by the polymer resin and the method of forming that product can ultimately determine the desired properties and attributes of the polymer. Mechanical properties include tensile, flexural, impact, creep, stress relaxation, and hardness tests. Physical properties include density, molecular weight, molecular weight distribution, melting temperature, glass transition temperature, crystallization melting temperature, density, stereoregularity, crack growth, long-chain branching, and rheological measurements.

This invention is also directed to and encompasses polymers (e.g., ethylene/α-olefin copolymers, ethylene homopolymers, etc.) produced by any of the polymerization processes disclosed herein. Articles of manufacture may be formed from, and/or may comprise, the polymers produced in accordance with this invention.

Olefin monomers

Unsaturated reactants that can be employed with catalyst compositions and polymerization processes of this invention typically may include olefin compounds having from 2 to 30 carbon atoms per molecule and having at least one olefinic double bond. This invention encompasses homopolymerization processes using a single olefin, such as ethylene or propylene, as well as copolymerization, terpolymerization, etc. reactions using an olefin monomer with at least one other olefinic compound. For example, the resulting ethylene copolymers, terpolymers, etc. may generally contain a major amount of ethylene (mole percent >50) and a minor amount of comonomer (mole percent <50), although this is not a requirement. Comonomers that can be copolymerized with ethylene often may have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms, in their molecular chain.

In this invention, acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched, substituted, unsubstituted, functionalized and non-functionalized olefins can be used. For example, typical unsaturated compounds that can be polymerized with the catalyst compositions of this invention can include, but are not limited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, the four normal octenes (e.g., 1-octene), the four normal nonenes, the five normal decenes, and the like, or mixtures of two or more of these compounds. Cyclic and bicyclic olefins, including, but not limited to, cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like, can also be polymerized as described herein. Styrene can also be employed as a monomer in the present invention. In one aspect, the olefin monomer may comprise a C2-C20 olefin; alternatively, a C2-C20 alpha-olefin; alternatively, a C2-C10 olefin; alternatively, a C2-C10 alpha-olefin; alternatively, the olefin monomer may comprise ethylene; or alternatively, the olefin monomer may comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefin monomer and the olefin comonomer may independently comprise, for example, a C2-C20 alpha-olefin. In some aspects, the olefin monomer may comprise ethylene or propylene, which is copolymerized with at least one comonomer (e.g., a C2-C20 alpha-olefin, a C3-C20 alpha-olefin, etc.). In accordance with one aspect of this invention, the olefin monomer used in the polymerization process may comprise ethylene. In this regard, examples of suitable olefin comonomers may include, but are not limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and the like, or combinations thereof. According to another aspect of the present invention, the olefin monomer may comprise ethylene, and the comonomer may comprise a C3-C10 alpha-olefin; Alternatively, the comonomer may comprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, or any combination thereof; alternatively, the comonomer may comprise 1-butene, 1-hexene, 1-octene, or any combination thereof; alternatively, the comonomer may comprise 1-butene; alternatively, the comonomer may comprise 1-hexene; or alternatively, the comonomer may comprise 1-octene.

In general, the amount of comonomer introduced into a polymerization reactor system to produce a copolymer may be from about 0.01 to about 50 weight percent of the comonomer based on the total weight of the monomer and comonomer. In another aspect of the present invention, the amount of comonomer introduced into a polymerization reactor system may be from about 0.01 to about 40 weight percent of comonomer based on the total weight of the monomer and comonomer. In yet another aspect, the amount of comonomer introduced into a polymerization reactor system may be from about 0.1 to about 35 weight percent of comonomer based on the total weight of the monomer and comonomer. Likewise, in another aspect, the amount of comonomer introduced into a polymerization reactor system may be from about 0.5 to about 20 weight percent of comonomer based on the total weight of the monomer and comonomer.

Although it is not intended to be bound by this theory, when branched, substituted, or functionalized olefins are used as reactants, it is believed that steric hindrance may impede and/or slow the polymerization process. Therefore, the cyclic and/or branched portion(s) of the olefin partially removed from the carbon-carbon double bond would not be expected to impede the reaction in the way that the same olefin substituents located closer to the carbon-carbon double bond would.

In accordance with one aspect of the present invention, at least one monomer/reactant may be ethylene (or propylene), such that the polymerization reaction may be a homopolymerization involving only ethylene (or propylene), or a copolymerization with a different acyclic, cyclic, terminal, internal, linear, branched, substituted, or unsubstituted olefin. Furthermore, the catalyst compositions of this invention may be used in the polymerization of diolefin compounds including, but not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Polymers and articles

The olefin polymers encompassed herein may include any polymer produced from any olefin monomer and comonomer(s) described herein. For example, the olefin polymer may comprise an ethylene homopolymer, a propylene homopolymer, an ethylene copolymer (e.g., ethylene/α-olefin, ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), a propylene copolymer, an ethylene terpolymer, a propylene terpolymer, and the like, including combinations thereof. In one aspect, the olefin polymer may be (or may comprise) an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer, or alternatively, an ethylene/1-hexene copolymer. In another aspect, the olefin polymer may be (or may comprise) a polypropylene homopolymer or a propylene-based copolymer.

If the resulting polymer is, for example, an ethylene polymer, its properties can be characterized by various analytical techniques known and used in the polyolefin industry. Articles of manufacture can be formed from and/or comprise the ethylene polymers of this invention, typical properties of which are provided below.

Generally, the density of the ethylene polymer (e.g., ethylene homopolymer and/or ethylene/α-olefin copolymer, such as, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octene copolymer) may range from about 0.87 to about 0.96 g/cm. In one aspect of this invention, the density of the ethylene polymer may be in a range of about 0.89 to about 0.96, or from about 0.87 to about 0.94 g/cm. In yet another aspect, the density may be in a range of about 0.90 to about 0.96 g/cm, such as, for example, from about 0.91 to about 0.96 g/cm, from about 0.91 to about 0.95 g/cm, or from about 0.91 to about 0.94 g/cm.

Suitable non-limiting ranges for the melt index (MI) of the ethylene polymer may include an MI of less than or equal to about 25, less than or equal to about 10, less than or equal to about 5, or less than or equal to about 2 g/10 min. In some aspects, the ethylene polymer may have an MI in a range of from 0 to about 25, from about 0.1 to about 10, from about 0.25 to about 5, from about 0.5 to about 3, or from about 0.5 to about 2 g/10 min.

Although not limited thereto, the ethylene polymer may have a number average molecular weight (Mn) in a range of about 5,000 to about 150,000, about 5,000 to about 50,000, about 10,000 to about 100,000, or about 15,000 to about 75,000 g/mol. Additionally or alternatively, the ethylene polymer may have a weight average molecular weight (Mw) in a range of about 50,000 to about 700,000, about 60,000 to about 600,000, about 75,000 to about 500,000, or about 100,000 to about 400,000 g/mol.

Ethylene polymers, whether homopolymers, copolymers, etc., can be formed into various articles of manufacture. Articles that may comprise polymers of this invention include, but are not limited to, an agricultural film, an automotive part, a bottle, a drum, a fiber or fabric, a film or container for food packaging, a food service article, a fuel tank, a geomembrane, a household container, a liner, a molded product, a medical device or material, a pipe, a sheet or tape, a toy, and the like. Various processes can be employed to form these articles. Non-limiting examples of these processes include injection molding, blow molding, rotational molding, film extrusion, sheet extrusion, profile extrusion, thermoforming, and the like. Additionally, additives and modifiers are often added to these polymers to provide favorable attributes for polymer processing or the end-use product. These processes and materials are described in Modern Plastics Encyclopedia, Mid-November 1995, Vol. 72, No. 12; and Film Extrusion Manual - Process, Materials, Properties, TAPPI Press, 1992.

Also contemplated by this invention is a method for forming or preparing an article of manufacture comprising a polymer produced by any of the polymerization processes disclosed herein. For example, the method may comprise (i) contacting a catalyst composition with an olefin monomer and an optional olefin comonomer in a polymerization reaction system under polymerization conditions to produce an olefin polymer, wherein the catalyst composition may comprise a metallocene compound, a fluorinated solid oxide activator, and an optional cocatalyst (e.g., an organoaluminum compound); and (ii) forming an article of manufacture comprising the olefin polymer. The forming step may comprise compounding, melt processing, extrusion, molding or thermoforming, and the like, including combinations thereof.

Examples

The invention is further illustrated by the following examples, which should not be construed in any way as imposing limitations on the scope of this invention.

The melt index (MI, g/10 min) can be determined according to ASTM D1238 at 190°C using a weight of 2,160 grams, and the high-load melt index (HLMI, g/10 min) can be determined according to ASTM D1238 at 190°C using a weight of 21,600 grams. The density can be determined in grams per cubic centimeter (g/cm3) on a compression-molded specimen cooled at 15°C per hour and conditioned for 40 hours at room temperature according to ASTM D1505 and ASTM D4703.

Molecular weights and molecular weight distributions were obtained using a PL-GPC 220 system (Polymer Labs, an Agilent company) equipped with an IR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns (Waters, MA) operating at 145 °C. The flow rate of the 1,2,4-trichlorobenzene (TCB) mobile phase containing 0.5 g/L of 2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymer solution concentrations were within the range of 1.0–1.5 mg/mL, depending on the molecular weight. Sample preparation was carried out at 150 °C for a theoretical 4 h, with occasional gentle agitation, before the solutions were transferred into sample vials for injection. An injection volume of approximately 200 pL was used. The integral calibration method was used to derive molecular weights and molecular weight distributions using a Chevron Phillips Chemical Company HDPE polyethylene resin, MARLEX® BHB5003, as a standard. The integral table of the standard can be predetermined in an independent SEC-MALS experiment. Mn is the number-average molecular weight, Mw is the weight-average molecular weight, and Mz is the z-average molecular weight.

Rheological characterizations of the melt were performed as follows. Oscillatory shear measurements for small strains (10%) were carried out on an Anton Paar MCR 501 rheometer using parallel-plate geometry. All rheological tests were performed at 190 °C. The complex viscosity data |n*| versus frequency (w) were then curve-fitted using the modified three-parameter empirical Carreau-Yasuda (CY) model to obtain the zero shear viscosity (n*), the characteristic viscous relaxation time (Tn), and the amplitude parameter (a) (CY parameter-a). The simplified empirical Carreau-Yasuda (CY) model is as follows: ;; ;;; where: |n*(w)| = magnitude of complex shear viscosity;

n0= zero shear viscosity;

Tn= viscous relaxation time (Tau(n) in seconds);

a= "amplitude" parameter (CY-a parameter);

n = sets the final slope of the power law, set at 2/11; and

w= angular frequency of oscillatory shear deformation.

Details of the significance and interpretation of the CY model and derived parameters can be found in: C. A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321 (1989); C. A. Hieber and H. H. Chiang, Polym. Eng. Sci., 32, 931 (1992); and R. B. Bird, R. C. Armstrong, and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987).

The d50 particle size, or median or average particle size, refers to the particle size for which 50% of the sample is smaller and 50% is larger. The particle size distribution (including d10, d50, and d90) was determined using laser diffraction in accordance with ISO 13320.

The BET surface areas disclosed herein were determined using the BET nitrogen adsorption method of Brunaur et al., J. Am. Chem. Soc., 60, 309 (1938). Total pore volumes were determined according to Halsey, G.D., J. Chem. Phys. (1948), 16, p. 931.

Examples A1-A2

Preparation of solid fluorinated oxide

For Example A1, a fluorinated solid oxide was produced using HBF4, and for Example A2, a fluorinated solid oxide was produced using H2SiF6. ZnO was used as the inorganic base and the solid oxide was silica-coated alumina (Siral® 40), containing 40% by weight silica and 60% by weight alumina. Recipe calculations for (A1) tetrafluoroboric acid (HBF4) and (A2) hexafluorosilicic acid (H2SiF6) are shown in Table I for 5% by weight F, or 5 grams of F per 100 grams (dry weight) of the solid oxide. About 1.25 equivalents of ZnO were used for each equivalent of acid, and after the addition of the solid oxide, the percent solids in the aqueous mixture was 20% by weight.

For these examples, water was first charged to the vessel, followed by the fluorine-containing acid compound and then the ZnO, and stirred until dissolved, which took approximately 10 minutes. If desired, an acid-base indicator (e.g., methyl orange) can be added to confirm that sufficient ZnO has been added to achieve a generally neutral pH, in this case, a pH value of approximately 4.5. Depending on the particular conditions, not all of the ZnO may dissolve. After the ZnO addition was complete, the solid oxide was added and mixed for 30 minutes at 25 °C to form an aqueous suspension. The fluorinated solid oxides were subsequently spray-dried.

Table I. Preparation of fluorinated solid oxide

Examples A3-A4

Preparation of solid fluorinated oxide with an additional metal.

Example A3 is the fluorinated solid oxide of Example A1 with additional zinc impregnation, and Example A4 is the fluorinated solid oxide of Example A2 with additional zinc impregnation. The protocol used to prepare Examples A3-A4 was the same as for Examples A1-A2, except that in Examples A3-A4, after the addition of ZnO was complete, an additional amount of zinc acetate was added, for a total amount of Zn of approximately 1 mmol/g of the solid oxide, as shown in Table II.

Table II. Preparation of fluorinated solid oxide with additional metal

Examples 1-15 and C1-C6

Polymerization experiments with fluorinated solid oxides.

For Examples 1-14 and C1-C5, the general procedure for the polymerization experiments was as follows. The polymerization experiments are summarized in Table III and were carried out in a 2.2 L autoclave reactor, with isobutane (1.2 L) used in all experiments. The fluorinated solid oxide, TIBA solution, and 3 mg of the metallocene compound (which was 1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl) methane zirconium dichloride, a cyclopentadienyl-fluorenyl bridged metallocene compound with one carbon bridge substituted by a methyl and a terminal butenyl) were charged to the reactor, followed by the addition of isobutane. An excess of the metallocene was used to allow the activity of the fluorinated solid oxide to be assessed. The reactor contents were stirred and heated to the desired polymerization reaction temperature of 95°C. Ethylene was then introduced into the reactor (no hydrogen or comonomer was added) and ethylene was fed on demand to maintain the target pressure of 2.76 MPa (400 psig) for the desired reaction time. The reactor was maintained at 95°C throughout the process by an automatic heating and cooling system. After venting the reactor, purging, and cooling, the resulting polymer product was dried under reduced pressure. For Examples 15 and C16, a 4-L steel reactor with 2 L of isobutane was used, but only 1 mg of the metallocene compound was used.

The fluorinated solid oxides for Examples 1-15 were prepared as generally described in Examples A1-A4, except that the ZnO was first combined with water, followed by the addition of the fluorine-containing acidic compound, which was neutralized by the ZnO (to a pH in the range of 4-5). Most, if not all, of the ZnO dissolved. For Examples 3-4, additional zinc acetate was added to the aqueous mixture. The silica-coated alumina (40 wt % silica) was then added and mixed for 30 minutes at 25 °C, followed by spray drying at about 100 °C. After drying, the catalyst was calcined for 3 hours in air at the respective maximum calcination temperature shown in Table III.

FIG. 1 depicts the particle size distribution of the fluorinated solid oxide product of Example 15 and, in summary, the fluorinated solid oxide product (fluorinated silica coated alumina) had a d10 of 17 pm, a d50 of 49 pm and a d90 of 78 pm.

FIG. 2 is a scanning electron micrograph of the fluorinated solid oxide of Example 15. As shown in FIG. 2, both fluorine and zinc are well distributed on the surface of the fluorinated solid oxide, demonstrating a homogeneous distribution and efficient use of both fluorine and zinc components in the production of the fluorinated solid oxide.

The fluorinated solid oxides for control examples C1-C3 were produced by contacting silica-coated alumina with an acidic HF solution, allowing fluorine to absorb onto the solid oxide, and then spray-drying in a commercial spray dryer. The d50 particle size was 37 pm.

The fluorinated solid oxides for Control Examples C4-C6 were produced by impregnating silica-coated alumina with either ammonium bifluoride solution (C4 and C6) or HBF4 solution (C5) in methanol (no inorganic base addition), drying, and then calcining for 3 hours as shown in Table III. Examples C4-C5 were spray-dried, while C6 was oven-dried.

For the preparation of fluorinated solid oxide, Table III summarizes the spray drying and calcination conditions, the fluorine compound used and the amount (mmol per gram of solid oxide), the amount of ZnO, the amount of zinc acetate (if used), and the surface area (SA) and total pore volume (PV) of the fluorinated silica-coated alumina. For the polymerization experiments, Table III summarizes the amount of TIBA (triisobutylaluminum) cocatalyst, the amount of fluorinated silica-coated alumina (FSCA), the amount of polyethylene produced (g), the reaction time (min), the catalyst yield (grams of PE per gram of FSCA), and the catalyst activity (grams of PE per gram of FSCA per hour).

Examples C1-C3 demonstrate typical catalyst activity—an average of 8,600 g/g/h—when using standard HF-produced FSCA. Using fluorinated solid oxides produced as described herein, Examples 1 through 14 used laboratory spray drying, and the data appears to indicate that a calcination temperature slightly higher than 650 °C results in increased catalyst activity, as opposed to the standard 600 °C used for C1-C3. Importantly, the examples calcined at 650 °C showed comparable, if not higher, activity—an average of 9,900 g/g/h—than Examples C1-C3.

To determine the impact of ZnO (inorganic base) on catalyst activity, Examples C4-C5 were produced using a standard ammonium bifluoride as the fluoride source and with an HBF4 fluoride source (as in Examples 1-14), but both without the addition of zinc. While the primary intent of the inorganic base addition is not related to catalyst activity, it appears that the addition of ZnO resulted in a slight increase in catalyst activity.

Example 15 was a larger-scale evaluation of FSCA, using spray drying and calcination in pilot plant facilities, and was tested under different polymerization conditions, resulting in lower catalyst activity than Examples 1-14. Example C6 provides a control catalyst run under these same conditions, demonstrating that the catalyst activity of Example 15 is much higher.

In summary, these examples indicate that the processes described for manufacturing fluorinated solid oxides result in an activator comparable to, if not superior to, standard fluorinated solid oxide activators produced by other processes. However, the advantage is that these fluorinated solid oxides can be produced at a relatively neutral pH (>4) without the emission of potentially hazardous and corrosive hydrogen fluoride fumes.

Examples 16-23: Preparation of fluorinated solid oxide with a sodium base.

Silica-coated alumina (Siral® 40) was impregnated with hydrofluoric acid to 5% F, and sodium carbonate was added in aqueous form to neutralize the acid, in an amount equal to the sodium level shown in Table IV. Sodium was added to neutralize the acidity during the preparation of fluorinated silica-coated alumina (FSCA). These FSCA supports were then calcined in air at 600 °C for three hours, cooled to room temperature, and flushed with dry nitrogen for 30 minutes. A 100 mg sample of each FSCA was placed into a 4-L stainless steel autoclave, along with 0.4 mL of triisobutylaluminum (TIBA) and 0.2 mg of a bridged metallocene compound (1-(methyl)-1-(3-butenyl)-1-(cyclopentadienyl)-1-(2,7-di-tert-butylfluorenyl) methane zirconium dichloride, a cyclopentadienyl-fluorenyl bridged metallocene compound with one carbon bridge substituted with a methyl and a terminal butenyl). Two liters of liquid isobutane were then added, and the reactor temperature was raised to 90 °C and maintained at that temperature throughout the experiment. Ethylene was added at 2.69 MPa (390 psig) and supplied on demand at that pressure for 30 minutes. After venting, purging and cooling the reactor, the resulting polymer product was dried under reduced pressure.

Table IV summarizes the results of Examples 16-23. Activity was calculated from the amount of polymer produced per gram of FSCA and the allotted time. The addition of sodium changed the molecular weight and rheological properties of the polymer produced. Although sodium carbonate reduced the acidity, it also unacceptably reduced catalyst activity as increasing amounts of sodium were added.

Examples 24-30

Preparation of solid fluorinated oxide with magnesium.

In Examples 24-30, the same procedure as in Examples 16-23 was used, except that magnesium nitrate, instead of a sodium base, was added during the preparation of the FSCA. After preparation, the FSCA supports were dried and calcined at 475 °C, followed by polymerization experiments identical to Examples 16-23. Table V summarizes the results of Examples 24-30. Unexpectedly, the activity was not affected by the addition of magnesium nitrate, regardless of the amount added. Furthermore, the polymer molecular weight and rheological properties were unaffected.

Examples 31-32

Preparation of fluorinated solid oxide with different magnesium bases.

For Example 31, 6.9 mL of a 22.5 wt % H2SiF6 solution was added to 30 mL of water, producing an acidic solution having a pH of about 1.0. To neutralize the acidity, magnesium carbonate was added, generating CO2 gas. The addition was continued until gas generation stopped, which occurred at 2.2 g of MgCO3, which is about 2 moles of Mg per mole of acid H2SiF6 used. The addition of magnesium carbonate raised the pH of the resulting mixture to a pH of about 5.1. Then, 30 g of Siral® 40 silica-coated alumina was added to this mixture. After mixing for 5 minutes, the FSCA was removed, dried in a vacuum oven at 110 °C overnight, and passed through a 35 mesh sieve. A 10-g sample of this powder was then calcined in a fluidized bed at 600 °C for three hours, in a manner similar to Examples 16-23. Polymerization experiments identical to Examples 16-23 were then performed using 100 mg of FSCA, 0.4 mL of 1 M TIBA, and 2 mg of the bridged metallocene. For Example 31, three experiments were performed with the FSCA prepared using MgCO3, and unexpectedly high activities were obtained: 7160 g/g/h, 7600 g/g/h, and 7740 g/g/h.

For Example 32, the same procedure as Example 31 was used except that the same molar amount of Mg was introduced into the hexafluorosilicic acid in the form of magnesium hydroxide. The polymerization conditions were the same. Two experiments were performed with the FSCA prepared using Mg(OH)2 and, similarly to Example 31, unexpectedly high activities were obtained for Example 32: 6840 g/g/h and 6400 g/g/h.

Claims (15)

1. A process for producing a solid fluorinated oxide, the process comprising: (a) contacting a fluorine-containing acid compound and an inorganic base to produce an aqueous mixture having a pH of at least about 4; and (b) contacting a solid oxide with the aqueous mixture to produce the fluorinated solid oxide. 2. The process of claim 1, wherein: the fluorine-containing acid compound and the inorganic base are contacted in an acid:base equivalent ratio in a range of about 1:1 to about 1:2; and the fluorine-containing acid compound is contacted first with water and then with the inorganic base to produce the aqueous mixture in step (a), or the inorganic base is contacted first with water and then with the fluorine-containing acid compound to produce the aqueous mixture in step (a). 3. The process of claim 1 or 2, wherein: a metal-containing compound is contacted with the fluorine-containing acid compound and the inorganic base in step (a); and The fluorinated solid oxide contains from about 0.5 to about 10% by weight of the metal of the metal-containing compound, based on the weight of the fluorinated solid oxide. 4. A process for producing a solid fluorinated oxide, the process comprising: (A) contacting a fluorine-containing acidic compound with a solid oxide to produce a mixture; and (B) contacting the mixture with an inorganic base to produce the fluorinated solid oxide at a pH of at least about 4. 5. The process of claim 4, wherein the process comprises an acid:base equivalent ratio of the fluorine-containing acid compound to the inorganic base in a range of about 1:1 to about 1:2. 6. The process of claim 4 or 5, wherein: A metal-containing compound is contacted with the mixture and the inorganic base in step (B); and the fluorinated solid oxide contains from about 0.5 to about 10% by weight of the metal in the metal-containing compound, based on the weight of the fluorinated solid oxide. 7. The process of any one of the preceding claims, wherein the inorganic base comprises a zinc-containing inorganic base, an aluminum-containing inorganic base, an iron-containing inorganic base, a manganese-containing inorganic base, a calcium-containing inorganic base, a magnesium-containing inorganic base, or any combination thereof. 8. The process of any one of the preceding claims, wherein: The fluorine-containing acid compound comprises hydrogen fluoride (HF), ammonium bifluoride (NH4HF2), triflic acid (CF3SO3H), tetrafluoroboric acid (HBF4), hexafluorosilicic acid (H2SiF6), hexafluorophosphoric acid (HPF6), or any combination thereof; and The inorganic base comprises ZnO, Zn(OH)2, ZnCO3, Al(OH)3, AhO3, AlOOH, Fe2O3, Fe(OH)3, Fe(OH)2, MnO2, Mn(OH)2, Ca(OH)2, CaCO3, Mg(OH)2, MgCO3, or any combination thereof. 9. The process of any one of the preceding claims, wherein: the fluorine-containing acid compound comprises tetrafluoroboric acid (HBF4), hexafluorosilicic acid (H2SiF6), or both; the inorganic base comprises ZnO, Zn(OH)2, ZnCO3, or any combination thereof; and The fluorinated solid oxide contains from about 0.5 to about 15% by weight of Zn, based on the weight of the fluorinated solid oxide. 10. The process of any one of the preceding claims, wherein: the pH is in a range of about 4 to about 8; and The fluorinated solid oxide contains from about 0.5 to about 15% by weight of F, based on the weight of the fluorinated solid oxide and/or in which: The fluorinated solid oxide has a total pore volume of about 0.5 to about 2.5 mL/g, a BET surface area of about 150 to about 700 m2/g, and an average particle size (d50) of about 20 to about 100 microns; and The fluorinated solid oxide comprises fluorinated alumina, fluorinated titania, fluorinated zirconia, fluorinated magnesia, fluorinated boria, fluorinated silica-alumina, fluorinated silica-coated alumina, fluorinated silica-titania, fluorinated silica-zirconia, fluorinated alumina-boria or any combination thereof. 11. The process of any of the preceding claims, wherein the solid oxide comprises silica-coated alumina, preferably wherein the silica-coated alumina contains from about 25 to about 50% by weight of silica, based on the weight of the silica-coated alumina. 12. The process of any one of the preceding claims, further comprising a step of spray drying the fluorinated solid oxide, or further comprising a step of calcining the fluorinated solid oxide. 13. A process for producing a catalyst composition, the process comprising: (i) the process of any one of claims 1-11; (ii) drying and calcining the solid fluorinated oxide; and (iii) contacting the fluorinated solid oxide, a metallocene compound and a cocatalyst to form the catalyst composition. 14. The process of claim 13, wherein the catalyst activity of the catalyst composition is greater than about 4,000 grams of polyethylene per gram of the solid fluorinated oxide per hour, under slurry polymerization conditions, with a triisobutylaluminum cocatalyst, using isobutane as a diluent, and at a polymerization temperature of 95°C and a reactor pressure of 2.76MPa (400 psig). 15. An olefin polymerization process, the process comprising: (i) the process of any one of claims 1-11; (ii) drying and calcining the solid fluorinated oxide; (iii) contacting the fluorinated solid oxide, a metallocene compound and an optional cocatalyst to form a catalyst composition. (iv) contacting the catalyst composition with an olefin monomer and, optionally, an olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.